Methods - Synthesis & Techniques
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Modern Nucleophilic Aromatic Substitution
Francois Terrier (Autor)
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Wiley - Vch
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Modern Nucleophilic Aromatic Substitution - Francois Terrier
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Reseña del libro "Modern Nucleophilic Aromatic Substitution"
Preface Xi 1 The Snar Reactions: Mechanistic Aspects 1 1. 1 Introduction 1 1. 2 Activation Of The Aromatic System: Driving Force For Snar Reactions 5 1. 2. 1 Benzene And Related Arene Derivatives 5 1. 2. 2 Pyridine And Related Aza - Aromatics 11 1. 2. 3 Five - Membered Ring Heterocycles 15 1. 2. 4 Activation By Electron - Withdrawing Heterocyclic Units: The Superelectrophilic Dimension In Snar Substitutions 18 1. 3 Leaving Group, Nucleophile, Solvent, And Medium Effects 24 1. 3. 1 The Influence Of The Leaving Group 24 1. 3. 1. 1 Halogen Nucleofugality 24 1. 3. 1. 2 The Mobility Of The Nitro Group And Other Leaving Groups 28 1. 3. 2 The Influence Of The Nucleophile 31 1. 3. 2. 1 Basicity And Polarizability 31 1. 3. 2. 2 Ritchie And Mayrs Scales 36 1. 3. 3 The Influence Of The Solvent 38 1. 3. 3. 1 Snar Reactions Involving Anionic Nucleophiles 38 1. 3. 3. 2 Snar Reactions Involving Neutral Nucleophiles 42 1. 4 Effects Of Specific Structural Variations In The Activated Ring 46 1. 4. 1 Ortho Versus Para Activation: Hydrogen Bonding And Built - In Solvation 46 1. 4. 2 Reactivity At Unsubstituted Versus Substituted Ring Carbon Atoms: Side Processes 50 1. 5 Spectral Evidence For The Intermediacy Of - Complexes In Snar Reactions 52 1. 6 Base Catalysis In Snar Reactions 57 1. 6. 1 The Specific Base - General Acid Mechanism 61 1. 6. 2 The Rate - Limiting Proton - Transfer Mechanism 65 1. 7 Regioselectivity In Snar Reactions 68 1. 8 Asymmetric Snar Substitutions 73 1. 9 Concerted Snar Substitutions 76 1. 9. 1 Ring Activation And Feasibility Of Concerted Substitutions 76 1. 9. 2 Concerted Substitutions In Triazines 79 1. 10 Conclusion 83 References 84 2 Structure And Reactivity Of Anionic - Complexes 95 2. 1 Introduction 95 2. 2 Structural Features Of - Complexes 96 2. 2. 1 X - Ray Crystallography 96 2. 2. 2 Gas - Phase Meisenheimer Complexes 100 2. 2. 3 Nmr Spectroscopy 103 2. 2. 3. 1 Complexation At Unsubstituted Carbons 103 2. 2. 3. 2 Complexation At Substituted Carbons 114 2. 2. 3. 3 Complexation Versus Proton Abstraction 123 2. 3 Thermodynamics And Kinetics Of - Complex Formation 125 2. 3. 1 The Nature Of The Aromatic System 126 2. 3. 2 The Effect Of Ring Substituents 129 2. 3. 3 Nucleophilic Reactivity At Substituted Versus Unsubstituted Carbons: Steric Effects 135 2. 3. 3. 1 Relative Reactivities And Stabilities Of 1 - Substituted And 1, 1 - Disubstituted Complexes 135 2. 3. 3. 2 Isomeric Addition At Substituted And Unsubstituted Carbons Of Electron - Deficient Aromatics: Relevance To Nucleophilic Aromatic Substitution Processes 140 2. 3. 4 Intramolecular Additions: Spiro Complexes 145 2. 3. 5 Diadduct Formation: Meta Bridging 148 2. 3. 6 The Effect Of The Nucleophile 150 2. 3. 7 Solvent And Medium Effects 152 References 156 3 The Superelectrophilic Dimension In Snar And Related - Complexation Processes 163 3. 1 Introduction 163 3. 2 The Classical Domain Of Snar And Anionic - Complexation Reactivity 164 3. 3 Reaching The Superelectrophilic Dimension 167 3. 3. 1 The Reference Water Reaction 167 3. 3. 2 - Complexation With Weak Carbon Nucleophiles 172 3. 3. 3 From The Pkah2O Scale To Mayrs Electrophilicity (E) Scale 174 3. 3. 4 Oxidation Potentials As Descriptors Of The Superelectrophilic Dimension 180 3. 4 The Synthetic Potential Of - Complexation And Snar Reactivity In The Superelectrophilic Dimension 182 3. 4. 1 - Complexation Reactivity 182 3. 4. 2 The Synthetic Potential Of Snar Substitutions: Normal (Picl, Nbd - Cl) Versus Super (Dnbf - Cl, Dnbz - Cl) Electrophiles 186 3. 5 Origin Of The Superelectrophilicity Of Neutral 10 Heteroaromatics 196 References 198 4 Synthetic Aspects Of Intermolecular Snar Reactions 205 4. 1 Introduction 205 4. 2 Intermolecular Displacements Of A Nitro Group 206 4. 2. 1 P - , O - , And M - Dinitrobenzenes - Related Substrates 206 4. 2. 2 Mononitro - Substituted Benzenes And Heteroarenes 216 4. 2. 3 Dinitro - And Trinitro - Substituted Benzenes And Related Derivatives 228 4. 3 Intermolecular Displacements Of Halogen And Other Leaving Groups 236 4. 3. 1 The Effect Of The Leaving Group - Synthetic Implications 236 4. 3. 2 Snar Couplings With Monoactivated Arenes 242 4. 3. 3 Snar Couplings With Polyhaloaromatics 251 4. 3. 4 Snar Couplings With Strongly Activated Arenes 255 4. 3. 5 Snar Couplings With Aza And Polyaza Heteroaromatics 263 4. 4 Conclusion 269 References 271 5 Intramolecular Snar Reactions 279 5. 1 Introduction 279 5. 2 Snar Cyclizations 280 5. 2. 1 Substitutions With Oxygen Nucleophiles 280 5. 2. 2 Substitutions With Nitrogen Nucleophiles 290 5. 2. 3 Substitutions By Sulfur Nucleophiles 296 5. 2. 4 Substitutions By Carbon Nucleophiles 298 5. 2. 5 Intramolecular Snar Reactions In Macrocyclization 300 5. 3 Smiles Rearrangements 303 5. 3. 1 On And No Rearrangements 304 5. 3. 2 Nn Rearrangements 311 5. 3. 3 Oo Rearrangements 315 5. 3. 4 Ns And Sn Rearrangements 318 5. 3. 5 So And Seo Rearrangements 321 5. 3. 6 Rearrangements With C - C Bond Formation. Truce - Smiles Rearrangements 325 5. 4 Conclusion 331 References 332 6 Nucleophilic Aromatic Substitutions Of Hydrogen 337 6. 1 Introduction 337 6. 2 Reactions Involving Oxidation Of - Complex - Type Intermediates 339 6. 2. 1 Spontaneous Oxidations 339 6. 2. 2 Reactions Involving An External Oxidizing Agent (Onsh) 351 6. 2. 2. 1 Oxidation Of Oxygen - And Nitrogen - Bonded Adducts 353 6. 2. 2. 2 Oxidation Of Carbon - Based H Adducts 357 6. 2. 2. 3 Electrochemical Oxidation 372 6. 3 Vicarious Nucleophilic Aromatic Substitutions Of Hydrogen (Vns) 374 6. 3. 1 Vns Amination And Hydroxylation Processes 374 6. 3. 2 Vns Substitutions With Carbon Nucleophiles 378 6. 3. 2. 1 Effect Of The Structure Of The Nitroarene 379 6. 3. 2. 2 Effect Of The Structure Of The Carbanion 384 6. 4 Deoxygenative Snarh Substitutions 395 6. 5 Cine And Tele Substitutions 397 6. 5. 1 The Von Richter Rearrangement 398 6. 5. 2 O - Dinitro Six - Membered Ring Aromatics And Related Derivatives 400 6. 5. 3 M - Diactivated Arenes And Related Substrates 404 6. 5. 4 Cine And Tele Substitutions In Heterocyclic Series 407 6. 5. 4. 1 Aza And Polyaza Aromatics 407 6. 5. 4. 2 Five - Membered Ring Heteroaromatics 409 6. 6 Conclusion 414 References 415 7 Other Snar Substitution Pathways 423 7. 1 Sn(Anrorc) Substitutions 423 7. 1. 1 Introduction 423 7. 1. 2 Aza Aromatics Without Nitro Activation 423 7. 1. 3 Nitro - Activated Aza Aromatics 426 7. 1. 4 Conclusion 429 7. 2 Radical Nucleophilic Aromatic Substitutions 430 7. 2. 1 Introduction 430 7. 2. 2 Radical Anion Formation In Snar Systems 431 7. 2. 3 Representative Radical Nucleophilic Aromatic Substitutions 438 7. 2. 4 Substitutions Via Charge - Transfer Complexes Of Anionic Radical Character 445 7. 3 Nucleophilic Aromatic Photosubstitutions 448 7. 3. 1 General Features 448 7. 3. 2 Sn2Ar Reactions 450 7. 3. 3 Sn(Et)Ar Reactions 453 7. 3. 4 Sn1Ar Reactions 455 7. 3. 5 Regioselectivity And Chemical Theory 456 7. 3. 5. 1 The Frontier Molecular Orbital Theory 456 7. 3. 5. 2 The Energy Gap Model And Other Recent Approaches 458 References 459 Index 465
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